Photographic developing combinations

ABSTRACT

A PROCESS AND SOLUTION FOR DEVELOPING EXPOSED SILVER HALIDE EMULSIONS DURING A SUPER-ADDITIVE COMBINATION OF AN ANIONIC SILVER HALIDE DEVELOPER SUCH AS HYDROQUINONE OR A DERIVATIVE THEREOF AND A BIS(PYURIDONE) AZINE SUBSTITUTED ON THE NITROGEN ATOMS BY AN ALKYL OR AN ARALKYL GROUP. DEVELOPMENT IS CARRIED OUT UNDER ALKALINE CONDITIONS.

United States Patent Ofice 3,563,747 PHOTOGRAPHIC DEVELOPING COMBINATIONS Jozef Frans Willems, Wilrijk, Antoon Leon Vandenberghe, Hove, and George Frans van Veelen, Mortsel, Belgium, assignors to Gevaert-Agfa N.V., Mortsel, Belgium, a Belgian company No Drawing. Filed Nov. 6, 1967, Ser. No. 680,995 Claims priority, application Great Britain, Nov. 4, 1966, 49,658/ 66 Int. Cl. G03c 5/30, 5/54 US. Cl. 9666 9 Claims ABSTRACT OF THE DISCLOSURE A process and solution for developing exposed silver halide emulsions using a super-additive combination of an anionic silver halide developer such as hydroquinone or a derivative thereof and a bis[pyridone]azine substituted on the nitrogen atoms by an alkyl or an aralkyl group. Development is carried out under alkaline conditions.

The invention relates to the development of photographic 'materials, containing exposed silver halide, by means of new developing combinations.

It is known that the developing activity of a developing solution containing several developing substances can be higher than the sum of the developing activities of the separate developing solutions of each of these developing substances used in the same concentration as in the solution of the several developing substances. This phenomenon is called the superadditivity of developing substances.

The most common example of superadditive development is that of the combination of p-monomethylaminophenol hemisulphate and hydroquinone, which has been described by G. Pizzighelli, Leitfaden der praktischen Photographie, Auflage 14 (Paul Hanneke), p. 177.

It is further known from British Pat. No. 542,502 that the combination of hydroquinone and 1-phenyl-3-pyrazolidinone has a still more intense developing action than the combination of hydroquinone and p-monomethylaminophenol hemisulphate.

It has now been found that an exceptional superadditive developing activity is obtained, exceeding that of the combination of hydroquinone with p-monornethylaminophenol hemisulphate, when using in the developing of exposed silver halide emulsion layers a developing combination of an anionic developing agent such as hydroquinone, derivatives of hydroquinone and ascorbic acid, with a bis[pyridone]azine substituted in the l-positions by the same or different radical selected from alkyl including substituted alkyl and aralkyl including substituted aralkyl, or such an azine the pyridone nuclei of which are further substituted.

The bis[pyridone]azines of use in the superadditive developing combinations according to the present invention correspond more particularly to the following general formula:

wherein:

each of R and R the same or different, represents alkyl including substituted alkyl, or aralkyl including substituted aralkyl e.g. alkyl or aralkyl substituted by halogen, hydroxy, alkoxy, amino, carbamoyl and sulphamoyl,

each of n and n, the same or different, represents or 1, and

each of Z and Z the same or different, represents the 3,563,747 Patented Feb. 16, 1971 atoms necessary to close a pyridone nucleus including a substituted pyridone nucleus, e.g. pyridone substituted by alkyl, halogen, hydroxy, alkoxy, amino, monoalkylamino, dialkylamino, sulphonamido and carbonamido.

The bis[pyridone]azines of use according to the present invention can be applied in the form of free bases as well as in the form of their salts.

The following are preparations of exemplary bis [pyridoneJazines of use according to the present invention.

PREPARATION 1 l-ethyl-Z-pyridone azine dihydrochloride having the following structural formula:

l a s C2 s was prepared as follows:

(a) l-ethyl-2-pyridone azine was prepared as described hereinafter according to the method described by S. Hiinig et al., Ann. 676 (1964) 49.

To a solution of 55 g. (0.2 mole) of 1-ethyl-2-br0mopyridinium fluoroborate in cc. of water, 5 g. (0.1 mole) of hydrazine hydrate were added dropwise while stirring and keeping the temperature between 0 and 5 C. Then 40.4 g. (0.4 mole) of triethylamine were added dropwise. Upon cooling, l-ethyl-2-pyridone azine crystallized as red crystals. The product was recrystallized from methanol. Yield: 13 g. (54%). Melting point: 165 C.

(b) 1-ethyl-2-pyridone azine dihydrochloride was prepared by treating a solution of the free base in methanol with hydrochloric acid and then evaporating the solvent. Melting point: C.

PREPARATION 2 l-benzyl-Z-pyridone azine having the following structural formula:

CuHs C6115 CH2 CH2 l1 1% was prepared as follows:

1-methyl-4-pyridone azine having the following structural formula:

was prepared as follows:

To a solution of 12.75 g. (0.05 mole) of l-methyl-4- chloro-pyridinum iodide in 20 cc. of water, 1.25 g.

(0.025 mole) of hydrazine hydrate were added dropwise while stirring and keeping the temperature at 20- 25 C. After having kept the reaction mixture at 50 C. for 1 hour 20 cc. of N sodium hydroxide were added dropwise. Upon cooling 3 g. (56%) of 1-methyl-4-pyridone azine crystallized. After recrystallisation from ethanol 2.5 g. (46%) of product were obtained. Melting point: above 260 C.

PREPARATION 4 1=( 2-hydroxyetl1yl) -2-pyridone azine dihydrochloride having the follouing structural formula:

was prepared as follows:

9.3 g. (0.05 mole) of l,2-di(2-pyridyl)-hydrazine, dissolved in 100 cc. of anhydrous methanol and 8.8 g. (0.2 mole) of ethylene oxide were refluxed for 8 hours. The reaction mixture was then treated with alcoholic hydrochloric acid and evaporated till dry. The residue was treated with warm n-propyl alcohol. The insoluble product that remained upon filtering is the hydrochloride salt of l,2-di(2-pyridyl)-hydrazine. The filtrate was then treated with ethyl acetate. 6 g. of l-(2-hydroxyethyl)-2- pyridone azine dihydrochloride were obtained. Melting point: 120 C.

PREPARATION," 5

1-methyl-2-pyridone azine dihydrochloride having the following structural formula:

was prepared as follows:

To a solution of 34.7 g. (0.1 mole) of l-methyl-Z- iodopyridinium iodide in 350 cc. of water, 2.5 g. (00.5 mole) of hydrazine hydrate were added dropwise while stirring at 60 C. Then 20.2 g. (0.2 mole) of triethylamine were added dropwise whereby 1-methyl-2-pyri- ZIICl done azine crystallized. The red crystals have a melting point of 162 C. Yield: 50%. The dihydrochloride was obtained by addition of hydrochloric acid to an alcoholic solution of the free base and then evaporating the solvent till dry. The residue was recrystallized from methanol-ether. Yield: 5.7 g. Melting point: above 260 C.

PREPARATION 6 1-(3-sulphamoylpropyl)-2-pyridone azine having the following structural formula:

((EIIDaSOzNHz 4 PREPARATION 7 1-n-butyl-2-pyridone azine having the following structural formula:

was prepared as follows:

To a solution of 17 g. (0.05 mole) of l-n-butyl-Z- bromopyridinium iodide in cc. of water 1.25 g. (0.025 mole) of hydrazine hydrate was added dropwise with stirring. The temperature was kept at 2530 C. After 15 minutes 10.1 g. (0.1 mole) of triethylamine were added dropwise. Upon cooling l-n-butyl-Z-pyridone azine crystallized as red crystals. The product was recrystallized from methanol. Yield: 3.5 g. (45%). Melting point: 159 C.

PREPARATION 8 l-isopropyl-Z-pyridone azine having the following structural formula:

was prepared as follows:

To a solution of 7.4 g. (0.02 mole) of 1-isopropyl-2- iodopyridinium iodide in 75 cc. of water 0.5 g. (0.01 mole) of hydrazine hydrate was added dropwise with stirring. The temperature was kept at 70 C. After 30 minutes 5 g. (0.05 mole) of triethylamine were added dropwise at 70 C. Upon cooling l-isopropyl-Z-pyridone azine crystallized as red crystals. The product was recrystallized from n-hexane. Yield: 2 g. (74%). Melting point: 195 C.

PREPARATION 9 l-n-propyl-Z-pyridone azine having the following structural formula:

was prepared as follows:

To a solution of 14 g. (0.04 mole) of l-n-propyl-Z- iodopyridinium iodide in 150 cc. of water 1 g. (0.02 mole) of hydrazine hydrate were added dropwise with stirring. The temperature was kept at 60 C. Then, 10.1 g. (0.1 mole) of triethylarnine were added dropwise at 60 C. Upon cooling l-n-propyl-Z-pyridone azine crystallized as red crystals. The product was recrystallized from n-hexane. Yield: 3.3 g. (61%). Melting point: 142 C.

PREPARATION 10 1,5-dimethyl-2-pyridone azine dihydrochloride h ving the following structural formula:

was prepared as follows:

To a suspension of 1,5-dimethyI-Z-iodo-pyridinium iodide in 300 cc. of water 1.25 g. (0.025 mole) of hydrazine hydrate was added dropwise with stirring. The temperature was kept at 80 C. After minutes 50 cc. of 2 N sodium hydroxide were added dropwise. Upon cooling, 1,5-dimethyl-2-pyridone azine crystallized.

The dihydrochloride of 1,5-dirnethyl-2-pyridone azine was obtained by addition of etheric hydrochloric acid to an alcoholic solution of the free base. Yield: 2.5 g. (32%). Melting point: 260 C.

PREPARATION 11" l-methyl-l-ethyl-2-pyridone azine having the following structural formula:

(EH3 (lle e N N-N was prepared as follows:

To a solution of 7 g. (0.02 mole) of l-methyl-Z- iodopyridinium iodide in 70 cc. of water 4.2 g. (0.02 mole) of 1-ethyl-2-pyridone hydrazone dihydrochloride in 10 cc. of water were added dropwise at 60 C. Then, 16 cc. of 5 N sodium hydroxide were added dropwise. Upon cooling, 2.5 g. (55%) of 1-methy1-1'-ethyl-2-pyridone azine crystallized. Melting point: 159 C.

In addition to the developing combination of use according to the present invention, the developing bath can contain the usual ingredients e.g. buffer compositions which may comprise salts such as carbonates, borates, phosphates, bisulphites, sulphites, metabisulphites and acids such as boric acid and citric acid. Further the developing bath may contain potassium bromide and watersoftening agents such as polyphosphates and derivatives of ethylene diamine tetraacetic acid, antifogging agents and wetting agents as well as other compounds known in the photographic development technique.

The pH of the baths may vary within wide limits, preferably between 8 and 11 so that a quick and hard development or a slow and soft development can be obtained as well.

The ratio of anionic developing agent to a bis[pyridone] azine compound used in the present invention can be chosen in such a way that the combination is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having highly sensitive silver bromoiodide emulsion layers.

The ratio of anionic developing agent to a bis[pyridone] azine according to the invention may vary within wide limits. In most cases the ratio is chosen in such a way that the amount of anionic developer strongly outweighs the amount of the bis[pyridone] azines of use according to the invention.

A strong superadditive effect is obtained by using an amount of 50 to 300 mg. of bis[pyridone]azine developing agent described hereinbefore to an amount of about 5 g. of anionic developing agent per litre. Of course larger amounts of said bis[pyridone]azine compounds can be used, although the superadditive effect obtained with higher concentrations is not more considerable. Preferably 5 mg. to 2 g. of bis[pyridone]azine and from 2 to 20 g. of anionic developing agent per litre are used.

Combinations of developing agents used in this invention may also be applied together or separately in the baths and/ or in the light-sensitive material and/or in the image-receiving material used in the application of the silver complex diffusion transfer process, the principle of which is described in the British patent specifications 614,155 and 654,630 and in the German patent specification 887,733.

With regard to the combination 1-phenyl-3-pyrazolidinone/hydroquinone, the combinations of developers Example 1 Strips of a photographic material comprising a lightsenstive silver halide emulsion layer coated on a cellulose triacetate support, are exposed through a grey filter with a light-quantity (E) which corresponds to the shoulder part of the density/ log E curve.

For comparison purposes each of these film strips is developed at 20 C. in separate developing baths. One of them is developed in a bath A containing as developing agent only hydroquinone and having the following composition:

G. Sodium carbonate 20 Sodium hexametaphosphate 1 Sodium sulphite 20 Potassium bromide 0.5 Hydroquinone 4.4

Water to 1 litre.

Another strip is developed in a bath having the same composition as bath A but containing in addition thereto 100 mg. (0.617 millimole) of 1-phenyl-3-pyrazolidinone whereas the remaining strips are developed in baths having the same composition as bath A but containing in addition, as listed in Table I, 0.617 millimole of a compound corresponding to the above general formula. The densities are determined respectively after a developing time of 30 and 60 seconds.

TABLE I Density alter a development time of Developing bath 30 sec. 60 sec.

Bath A 0. 04. 0. 04 Bath A plus 100 mg. lf l-phenyl-3pyrazolidin0ne 0. 1. 70 Bath A plus 177 mg. of the compound of Preparation 5 1. 52 1. 90 Bath A plus 200 mg. of the compound of Preparation 1 1. 60 2. 10 Bath A plus 214 mg. of the compound of Preparation 4,- 1. 10 1. 80 Bath A plus 132 mg. of the compound of Preparation 3 0. 55 1. 20

When the above compounds corresponding to the above general formula are used in the given concentration in a developing bath A containing no hydroquinone, no density is obtained after the given development times.

Example 2 Strips of a photographic material comprising a lightsensitive silver halide emulsion layer, coated on a cellulose triacetate support, are exposed through a grey filter with a light-quantity (E) which corresponds to the shoulder part of the density/ log E curve.

For comparison purposes each of these film strips is developed at 20 C. in separate developing baths. One of them is developed in a bath B containing as developing agent only hydroquinone and having the following composition:

G. Boric acid 5 Borax 10 Sodium hexametaphosphate 1 Sodium sulphite Hydroquinone 4.4 Potassium bromide 0.5

Water up to 1000 cc.

The other strips are developed in baths having the same composition as bath B but containing in addition thereto as listed in Table II, 0.617 millimole of a compound corresponding to the above general formula. The densities are determined respectively after 2 min., 4 min., 6 min. and 8 min.

TABLE 111 Density after a development time of- Developing bath 30 sec. 60 sec.

Bath A O 0. 04 ()4 Bath A plus 50 mg. of 1-phenyl-3-pyrazolidiilone 0. 18 1. 30

Bath A plus 89 mg. of the compound of Preparation 1. 25 1 15 Bath A plus 100 mg. 01 the compound of Preparation 1. 1. 3 1. 85 Bath A plus 98 mg. of the compound of Preparation 10 1. 20 1. 85 Bath A plus 107 mg. of the compound of Preparation 4 0.50 1. 60

Example 4 This example is completely analogous to Example 2 with the difference however that the supplemental developing substance is used in a concentration of 0.31 millimole per litre of developing bath. The densities obtained after 2 min., 4 min., 6 min. and 8 min. respectively are listed in the table below.

TABLE IV Density after a development time oi- Developing bath 2 min. 4 min. 6 min. 8 min Bath B 0. 04 0. O4 0. 04 0. 04 Bath 13 plus 50 mg. 01 l-phenyl- 3-pyrazolidinone 0. 15 0. 95 1. 40 l. 55. Bath 13 plus 89 mg. of the compound of Preparation 5 0. 40 0.80 1. 10 1. 27 Bath B plus 100 mg. of the pound of Preparation 1 0. 55 0. 97 1.18 1. 30 Bath B plus 84 mg. of the compound ol Preparation 8 O. 85 1.30 1. 47 1. 60 Bath B plus 84 mg. of the compound of Preparation 9 0. 75 1. 22 1. 37 1. 50

Example 5 This example is completely analogous to Example 2 with the difference however that the supplemental developing substance is used in a concentration of 0.031 millimole per litre of developing bath. The densities obtained after 4 min., 16 min. and 32 min. respectively are listed in the table below.

TA B LE V Density after a development time ol Developing bath 4 min. 16 min. 32 min.

0. 04 0. 04 0.01 mg of dinone 0. 0i 0. 19 1. 51

9. mg. of the compound of Preparation 7 0. 1. 10 1. 43

Bath B plus 8.4 mg. of the compound of Preparation 8 0. 13 0. 1. 10

What we claim is:

1. Photographic developing method comprising developing under alkaline conditions an exposed silver halide emulsion layer of a light-sensitive photographic material with an anionic silver halide developing agent and a bis [pyridone] azine, substituted in the l-positiotns by the same or different group selected from an alkyl group and an aralkyl group.

2. Photographic developing method according to claim 1, wherein the bis[pyridone] azine corresponds to the following general formula:

wherein:

each of R and R the same or different, is an alkyl group or an aralkyl group,

each of n and n, the same or different, is 0 or 1, and

each of Z and Z the same or different, represents the atoms necessary to close a pyridone nucleus.

3. Photographic developing method according to claim 1, wherein said light-sensitive photographic material is a material for use in the silver complex diffusion transfer process and the exposed silver halide emulsion layer is developed while in intimate contact with a supported receiving layer for use in the silver complex diffusion transfer process.

4. Photographic developing method according to claim 1, wherein the anionic developing agent is hydroquinone or a derivative thereof.

5. An alkaline photographic developing solution for developing an exposed silver halide emulsion layer of a photographic material which solution comprises in addition to an anionic silver halide developing agent a his [pyridone] azine compound substituted in the l-positions by the same or different group selected from an alkyl group and an aralkyl group.

6. Photographic developing solution according to claim 5 containing per litre from 2 to 20 g. of said anionic developing agent and from 5 mg. to 2 g. of a said his [pyridone] azine compound.

7. Photographic developing solution according to claim 5, wherein the anionic developing agent is hydroquinone or a derivative thereof.

8. The developing method of claim 1 wherein said development is carried out at a pH of about 8 to 11.

9. A photographic developing solution as in claim 5 having a pH of about 8 to 11.

References Cited UNITED STATES PATENTS 3,266,899 8/1966 Ramsay 96-66 WILLIAM D. MARTIN, Primary Examiner M. SOFOCLEOUS, Assistant Examiner US. Cl. X.R. 96-29, 66.3 

